嵌套病例对照研究中的两步估计方法（英）

本文讨论嵌套病例对照研究中相对危险率的估计问题，引入了相对危险率的两步估计，并在一般嵌套病例对照抽样的假设下讨论了相对危险率的两步估计的相合性问题，最后给出了几个例子。     

不同倾角的脉管制冷机内自然对流影响的研究

本文通过对脉管内自然对流的数值模拟，讨论了当脉管冷端处在不同方向时，脉管内的自然对流对脉管制冷机性能的影响．数值模拟结果表明，当冷端在下时获得的制冷温度最低；当热端在下并与重力方向成３０°时制冷温度最高．结论与实验测量结果定性一致．所做的理论分析对实现脉管制冷机的良好运行有指导意义。     

双组元姿控发动机反流特性的DSMC模拟

为准确获得双组元姿控发动机的羽流及其反流特性,采用直接模拟蒙特卡罗(DSMC)方法结合可变软球(VSS)模型数值模拟以N2O4/MMH为推进剂的真空羽流。喷口参数由喷管流动的DSMC法计算得到。与文献比较表明本文计算程序可信。模拟结果表明,分子质量越小的气体越容易进入反流区;本文的计算条件下,在偏离X轴正向116°~140°范围内,组分数密度和质量流率以及温度均出现了最大值。     

Meshless simulation of equilibrium swelling/deswelling of pH‐sensitive hydrogels

Hydrogels have been widely used in microelectromechanical systems (MEMS) and Bio‐MEMS devices. In this article, the equilibrium swelling/deswelling of the pH‐stimulus cylindrical hydrogel in the microchannel is studied and simulated by the meshless method. The multi‐field coupling model, called multi‐effect‐coupling pH‐stimulus (MECpH) model, is presented and used to describe the chemical field, electric field, and the mechanical field involved in the problem. The partial differential equations (PDEs) describing these three fields are either nonlinear or coupled together. This multi‐field coupling and high nonlinear characteristics produce difficulties for the conventional numerical methods (e.g., the finite element method or the finite difference method), so an alternative—meshless method is developed to discretize the PDEs, and the efficient iteration technique is adopted to solve the nonlinear problem. The computational results for the swelling/deswelling diameter of the hydrogel under the different pH values are firstly compared with experimental results, and they have a good agreement. The influences of other parameters on the mechanical properties of the hydrogel are also investigated in detail. It is shown that the multi‐field coupling model and the developed meshless method are efficient, stable, and accurate for simulation of the properties of the stimuli‐sensitive hydrogel. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 326–337, 2006     

The response of microstructure to processing in a series of poly(siloxaneimide) copolymers

Poly(siloxaneimide) (PSI) segmented copolymers exhibit organized microdomains if the blocks are sufficiently incompatible. As with neat diblock and triblock copolymers, the processing route employed to prepare films of PSI materials is expected to influence the dimensions and/or morphology of the resultant microstructure. In this work, small-angle neutron scattering (SANS) is utilized to characterize the disordered microstructure found in films of a series of PSI copolymers which are subjected to solvent casting and various thermal treatments. Microstructural dimensions such as the periodicity and correlation length are deduced from the Teubner-Strey (TS) model for disordered microemulsions. The scattering intensity of each copolymer up to q = 5.0 nm^?1, where q is the scattering vector, is found to scale as q^?2.8+?0.1. Results indicate that processing the materials as cast films or as melt-pressed films allowed to cool slowly has a small, but discernible, effect on microstructural characteristics. SANS profiles of films quenched from elevated temperatures reveal a clear transition in microdomain periodicity, which correlates well with the glass transition temperature of the imide microphase in these and other materials of similar chemical structure. © 1993 John Wiley & Sons, Inc.     

Conformational and Configurational Determination in 1,1,4,4-Tetrafluoro-2-Propylidene-3-Methyl-6-Tert-Butyl-1,4-Disila-5-Cyclohexene

A complete assignment of the ¹H, ¹³C and ¹⁹F NMR spectra of 1,1,4,4-tetrafluoro-2-propylidene-3-methyl-6-tert-butyl-1,4-disila-5-cyclohexene 3, the product of the cycloaddition reaction between tetrafluorodisilacyclobutene 1 and cis, trans-2,4-hexadiene mediated by (n⁵-C₅H₅)Mn(CO)₃, has been made by means of various 2D NMR chemical shift correlation methods and selective heteronuclear decoupling techniques. An analysis of the three bond ¹³C-¹H coupling constants and two bond ¹³C-¹⁹F coupling constants and the molecular modeling results enabled the determination of the conformation and configuration of compound 3. The conformation of 3 provides insight into mechanistic details of the Mn-mediated cycloaddition.     

Effect of film thickness and supercooling on the performance of cholesteryl cinnamate liquid crystal capillary columns

Improved separations of the isomers of olefinic aliphatic insect pheromones were obtained on cholesteryl cinnamate glass capillary columns by operating in the supercooled temperature range of the liquid crystal. Capillary columns were prepared with varying film thickness of the stationary phase; choice of the correct film thickness ensured optimum retention for a wide range of compounds within the most effective temperature range of the liquid crystal. The deactivation procedures described made the liquid crystal columns suitable for separation of the geometric isomers of polar and nonpolar compounds.     

Properties and structures of porphyrexides

The molecular and crystal structures of porphyrexides, viz., 4-amino-2-imino-(1) and (Z)-2-amino-4-bromoimino-5,5-dimethyl-4,5-dihydro-1H-imidazole 1-oxyls (7), and their diamagnetic precursors were determined. Compound 1 is kinetically unstable because it is oxidized with atmospheric oxygen to form (E)-1,2-bis[1-amino-1-(cyanoimino)-2-methyl-propan-2-yl]diazene 1,2-dioxide. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–447, March, 2006.     

On the Landau-Teller approximation for energy exchanges with fast degrees of freedom

We revisit the Landau-Teller heuristic approach to adiabatic invariants and, following Rapp, use it to investigate the energy exchanges between the different degrees of freedom, in simple Hamiltonian systems describing the collision of fast rotating or vibrating molecules with a fixed wall. We critically compare the theoretical results with particularly accurate numerical computations (quite small energy exchanges, namely of one part over 10³⁰, are measured).     

A configuration interaction study of phosphine using bonded functions

A computational study is made of the effect of basis set upon the energy, properties and inversion barrier of the phosphine molecule. The calculations are performed at both the SCF and CI level. The flexibility of the double zeta basis is discussed in the light of the results.